CN1310899C - Benzopyrone compounds with pest killing and sterilizing activity and preparation and use - Google Patents

Benzopyrone compounds with pest killing and sterilizing activity and preparation and use Download PDF

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Publication number
CN1310899C
CN1310899C CNB2003101050796A CN200310105079A CN1310899C CN 1310899 C CN1310899 C CN 1310899C CN B2003101050796 A CNB2003101050796 A CN B2003101050796A CN 200310105079 A CN200310105079 A CN 200310105079A CN 1310899 C CN1310899 C CN 1310899C
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alkyl
hydrogen
alkoxy
aryl
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CN1616448A (en
Inventor
刘长令
关爱莹
李志念
李林
李正名
李淼
张明星
张弘
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Shenyang Sinochem Agrochemicals R&D Co Ltd
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Shenyang Research Institute of Chemical Industry Co Ltd
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Priority to CNB2003101050796A priority Critical patent/CN1310899C/en
Priority to EP04797287.2A priority patent/EP1683792B9/en
Priority to PCT/CN2004/001255 priority patent/WO2005044813A1/en
Priority to US10/573,529 priority patent/US7642364B2/en
Priority to JP2006538636A priority patent/JP4674672B2/en
Priority to CNB2004800201255A priority patent/CN100363356C/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7

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  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention relates to a novel benzopyrone derivate which is shown in a general formula (I) and is used as a biocidal agent and a germicidal agent. In the formula, A is CH or N, B is O, S or NR9, R9 is hydrogen or (C1 to C12) alkyl, R1 and R2 are hydrogen, C1 to C12 alkyl, or halogenating C1 to C12 alkyl, R3 is hydrogen, C1 to C12 alkyl, halogenating C1 to C12 alkyl, or C1 to C12 alkoxy, R4, R5, R6, R7 and R8 can be the same or can be different, and R4, R5, R6, R7 and R8 are hydrogen, halogen, cyan, nitro, C1 to C12 alkyl, C2 to C12 alkenyl, alkynyl, C1 to C12 halogenating alkyl, C1 to C12 alkoxy, C1 to C12 alkyl sulphide radical, C1 to C12 alkane sulfonyl, C1 to C12 alkyl carbonyl, C1 to C12 alkoxy, C1 to C12 alkyl, C1 to C12 alkoxy carbonyl, C1 to C12 alkoxy carbonyl, C1 to C12 alkyl, C1 to C12 halogenating alkoxy, C1 to C12 alkyl, optional substitute amido C1 to C12 alkyl, optional substitute aryloxy, optional substitute aroylation C1 to C12 alkyl oxy, optional substitute aryl, hetero aryl, optional substitute aryl C1 to C12 alkyl, hetero aryl C1 to C12 alkyl, hetero aryl C1 to C12 alkoxy, and groups represented in the following general formula. R10 and R11 are hydrogen, optional substitute alkyl, optional substitute aryl, and optional substitute aryl (C1 to C12) alkyl.

Description

Benzofurantone compound and preparation and application with desinsection, fungicidal activity
Technical field
The invention belongs to agricultural insecticidal, sterilant.
Background technology
Natural product benzopyrone and methoxy acrylate compound all are compounds of known biologically active.Document JP 04-182461 once disclosed the compound of following general formula:
The structural chemistry of disclosed compound 51 is as follows in this patent:
There is not to disclose the activity data of this compound in the document.We find that by synthesizing and giving birth to survey this compound activity is lower.
Summary of the invention
In order to obtain under very little dosage, just can control the active compound of various diseases, insect pest, inventors of the present invention have synthesized a kind of novel Benzofurantone compound, this compounds has broad spectrum of activity---can be used for control on various crops by multiple germ diseases such as Oomycete, Basidiomycetes, ascomycetes and imperfect fungis, and because these compounds have very high biological activity makes just can obtain good effect under very low dosage.This compounds all has good preventive effect to diseases such as downy mildew of garpe, rice sheath blight disease, rice blast, early blight of tomato, tomato late blight, wheat rust, speckled leaf blotch, wheat powdery mildew, powdery mildew of cucumber, cucumber downy mildew, gray molds of cucumber.Amazing especially discovery is, compound of the present invention is effective to various pests such as mythimna separata, small cabbage moth, aphid, ladybug, evil mite and culex pipiens pollens, especially ladybug and culex pipiens pollens there are special efficacy, are very suitable for integrated control, thereby finished the present invention various pest on crop.
Novel Benzofurantone compound provided by the invention and steric isomer thereof, shown in general formula (I):
In the formula: A is selected from CH or N; B is selected from O, S or NR 9R 9Be selected from hydrogen or (C 1-C 12) alkyl; R 1, R 2Be selected from hydrogen, C respectively 1-C 12Alkyl or halo C 1-C 12Alkyl; R 3Be selected from hydrogen, C 1-C 12Alkyl, halo C 1-C 12Alkyl or C 1-C 12Alkoxyl group; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, any substituted amido C 1-C 12Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 12Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12The group that alkoxyl group and following general formula are represented:
Wherein: R 10, R 11The aryl C that is selected from hydrogen, the alkyl that replaces arbitrarily, the aryl that replaces arbitrarily respectively or replaces arbitrarily 1-C 12Alkyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NR 9
Comparatively preferred compound is among the present invention: A is selected from CH or N in the general formula (I); B is selected from O, S or NR 9R 9Be hydrogen or C 1-C 6Alkyl; R 1, R 2Be selected from hydrogen, C respectively 1-C 6Alkyl or halo C 1-C 6Alkyl; R 3Be selected from hydrogen, C 1-C 6Alkyl or halo C 1-C 6Alkyl, C 1-C 6Alkoxyl group; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6), alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6), alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl, any substituted amido C 1-C 6Alkyl, the aryloxy that replaces arbitrarily, any fragrant C that replaces 1-C 6Alkyl oxy, the aryl that replaces arbitrarily, heteroaryl, any aryl C that replaces 1-C 6Alkyl, heteroaryl (C 1-C 6) alkyl, heteroaryl C 1-C 6The group that alkoxyl group and following general formula are represented:
Wherein: R 10, R 11Be selected from hydrogen, the alkyl that replaces arbitrarily, the aryl that replaces arbitrarily, any aryl C that replaces respectively 1-C 6Alkyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NR 9
Further preferred compound is: A is selected from CH or N in the general formula (I); B is selected from O or NH; R 1, R 2Be selected from methyl; R 3Be selected from hydrogen or methyl; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6Alkoxy carbonyl C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, substituted amido C 1-C 3Alkyl, (replacement) phenoxy group, (replacement) benzyloxy, (replacement) phenyl, (replacement) benzyl, and the group represented of following general formula:
Figure C20031010507900053
Wherein: R 10, R 11Be selected from hydrogen or substituted alkyl respectively; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NH.
Further preferred compound is: A is selected from CH or N in the general formula (I); B is selected from O or NH; R 1, R 2Be selected from methyl; R 3Be selected from hydrogen or methyl; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, cyano group, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxyl group, C 1-C 6Alkoxy C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, substituted amido C 1-C 3The group that alkyl, (replacement) phenyl, (replacement) benzyl and following general formula are represented:
Figure C20031010507900054
R wherein 10, R 11Be methyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NH.
In the definition of the compound that provides above (I), compile the following substituting group of used term general proxy:
(replacement) phenoxy group, (replacement) benzyloxy, (replacement) phenyl, substituting group is a hydrogen in (replacement) benzyl, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro, CN or the like, substituent number can be 0～5.
Halogen: refer to fluorine, chlorine, bromine and iodine.
Alkyl: straight or branched alkyl, for example methyl, ethyl, propyl group, sec.-propyl and the tertiary butyl.
Haloalkyl: the straight or branched alkyl, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl.
Alkoxyl group: the straight or branched alkyl is connected on the structure through the Sauerstoffatom key.
Halogenated alkoxy: the straight or branched alkoxyl group, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom.For example, halogenated alkoxy such as chlorine methoxyl group, dichloro methoxyl group, trichlorine methoxyl group, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, chlorine fluorine methoxyl group.
Alkenyl: straight or branched also can have two key, for example vinyl, allyl groups on any position.The substituted alkenyl base comprises the aromatic yl alkenyl of any replacement.
Alkynyl: straight or branched also can have triple bond on any position, for example ethynyl, propargyl.Substituted alkynyl comprises the sweet-smelling alkynyl of any replacement.
Aryl moiety in aryl and aralkyl, aromatic yl alkenyl, sweet-smelling alkynyl, aryloxy and the aryloxy alkyl comprises phenyl and Nai Ji.
The indication heteroaryl is to contain one or more N, O, the heteroatomic 5 yuan of rings of S or 6 yuan of rings among the present invention.For example pyridine, furans, pyrimidine, pyrazine, pyridazine, triazine, quinoline, cumarone.
In compound of the present invention, because carbon-to-carbon double bond is connected different substituting groups and can forms geometrical isomer (representing different configurations with Z and E respectively) with the two keys of carbon-nitrogen.The present invention includes the mixture of Z type isomer and E-isomer and any ratio thereof.
Can the present invention be described with the compound of listing in the following Table I, but not limit the present invention.
Table 1
Figure C20031010507900061
R wherein 1, R 2=CH 3E is C (CH 3)=NOCH 3M is C 6H 3-3,4-(OCH 3) 2
Numbering A B R 3 R 4 R 5 R 6 R 7 R 8 Rerum natura *
1 CH O H H H H H H Oily
2 CH O H H CH 3 H H H 140～143
3 CH O H H CH 3 H H CH 3 188-190
4 CH O H H C 6H 5 H H CH 3 146-148
5 CH O H CH 3 CH 3 H H H 120～122
6 CH O H CH 3 CH 3 H H CH 3 174～176
7 CH O H H CF 3 H H H 164～166
8 CH O H H CH 3 H H E Oily
9 CH O H H CH 3 H E H 183～185
10 CH O H H CH 3 H COCH 3 H 169～172
11 CH O H H CH 3 H H COCH 3 165～167
12 CH O H Cl CH 3 H H H 162-164
13 CH O H H CH 2Cl H H H
14 CH O H Cl CH 2Cl H H H
15 CH O H Cl CH 2OCH 3 H H H
16 CH O H Cl CH 2CH 3 H H H
17 CH O H H CH 2CH 3 H H CH 3 154-156
18 CH O H C 2H 5 CH 3 H H H
19 CH O H H CH 2OCH 3 H H H
20 CH O H H CH 2OC 2H 5 H H H
21 CH O H Cl CH 2OC 2H 5 H H H
22 CH O H OCH 3 CH 2OCH 3 H H H
23 CH O H N(CH 3) 2 CH 3 H H H
24 CH O H CN H H H H 166-168
25 CH O H Cl CH 3 H H CH 3 202-204
26 CH O H H CH(CH 3) 2 H H H 128-130
27 CH O H C 3H 7 CH 3 H H H 142-144
28 CH O H H tC 4H 9 H H H
29 CH O H H 4-Cl-C 6H 4 H H H
30 CH O H Cl 4-Cl-C 6H 4 H H H
31 CH O H H 4-Cl-C 6H 4 H H CH 3
32 CH O H Cl C 6H 5 H H H 142-144
33 CH O H H CH 2CH 3 H H H 134-136
34 CH O H H CH 2C 2H 5 H H H 118-120
35 CH O H H CH 2C 2H 5 H H CH 3 146-148
36 CH O H Cl CH 2C 2H 5 H H H 118-120
37 CH O H CH 3 CH 2C 2H 5 H H H
38 CH O H H 4-F-C 6H 4 H H H
39 CH O H Cl 4-F-C 6H 4 H H H
40 CH O H H 4-F-C 6H 4 H H CH 3
41 CH O H H 4-CF 3-C 6H 4 H H H
42 CH O H Cl 4-CF 3-C 6H 4 H H H
43 CH O H Cl CH 2N(CH 3) 2 H H H
44 CH O H OCH 3 C 2H 5 H H H
45 CH O H OCH 3 CH 3 H H H
46 CH O H OC 2H 5 CH 3 H H H
47 CH O H H CH 2OCH 2CF 3 H H H
48 CH O H Cl CH 2OCH 2CF 3 H H H
49 CH O H F CF 3 H H H
50 CH O H F CH 3 H H H
51 CH O H H CH 2N(CH 3) 2 H H H
52 CH O H H C 6H 5 H H H 130-133
53 CH O H Cl Cl H H H
54 CH O H F Cl H H H
55 CH O H H CH 2OCH 2C 6H 5 H E H
56 CH O H OCH 3 4-Cl-C 6H 5 H H H
57 CH O H F 4-Cl-C 6H 5 H H H
58 CH O H H M H H H
59 CH O H Cl M H H H
60 CH O H Cl M H H CH 3
61 CH O H CH 3S CH 3 H H H
62 CH O H CH 3SO 2 CH 3 H H H
63 CH O H F F H H H
64 CH O H CH 3SO 2 Cl H H H
65 CH O H H 4-NO 2-C 6H 5 H H H
66 CH O H Cl 4-NO 2-C 6H 5 H H H
67 CH O H H 4-NO 2-C 6H 5 H H CH 3
68 CH O H PhCH 2 CH 3 H H H
69 CH O H PhCH 2 CH 3 H H CH 3
70 CH O H CF 3CH 2O C 3H 7 H H H
71 CH NH H CH 3 CH 3 H H H
72 CH NH H CH 3 CH 3 H H CH 3
73 CH NH H OCH 3 CF 3 CH 3 H H
74 CH NH H OCH 3 CH 3 F H E
75 CH NH H H CF 3 H H CH 3
76 CH NH H CH 3 CH 2Cl H H H
77 CH NH H CH 3 CH 2Cl H H CH 3
78 CH NH H Cl CH 2Cl H H H
79 CH NH H H M Cl H E
80 CH NH H H M H E H
81 CH NH H H M H COCH 3 H
82 CH NH H H M H H COCH 3
83 CH NH H Cl CH 2OCH 3 H H H
84 CH NH H H 4-C 6H 5Cl H H H
85 CH NH H H 4-C 6H 5Cl H H CH 3
86 CH NH H H CH 2OCH 3 H H CH 3
87 CH NH H CH 3 CH 2OCH 3 H H H
88 CH NH H CH 3 CH 2OCH 3 H H CH 3
89 CH NH H H CH 2OCH 3 H H H
90 CH NH H H CH 2OCH 3 H H E
91 CH NH H H CH 2OCH 2CF 3 H E H
92 CH NH H H CH 2N(CH 3) 2 H H H
93 CH NH H H CH 2OCH 2CF 3 H H COCH 3
94 CH NH H Cl CH 2OC 2H 5 H H H
95 CH NH H H CH 2OC 2H 5 H H H
96 CH NH H H CH 2OC 2H 5 H H CH 3
97 CH NH H H CF 3 H H CH 3
98 CH NH H CH 3 CF 3 H H H
99 CH NH H CH 3 Cl H H CH 3
100 N O H Cl CH 3 H H H 172-174
101 N O H H CH 3 H H H 150～152
102 N O H H CH 3 H H CH 3 178-180
103 N O H CH 3 CH 3 H H H 112～118
104 N O H F CH 3 H H H
105 N O H H CF 3 H H Cl
106 N O H CH 3 CH 3 H H CH 3 184～186
107 N O H H CH 3 H E CO 2CH 3
108 N O H H CH 3 H COCH 3 CO 2CH 3
109 N O H Cl CH 3 H H CH 3 198-200
110 N O H H CH 2Cl H H CO 2CH 3
111 N O H H H H H H 106～110
112 N O H H CH 2Cl H H CF 3
113 N O H H 3-CF 3-C 6H 4 H H CF 3
114 N O H CH 3 3-CH 3-C 6H 4 H H CF 3
115 N O H CH 3 4-CH 3-C 6H 4 H H CF 3
116 N O H H CH 2Cl H H H
117 N O H Cl CH 2Cl H H H
118 N O H Cl CH 2F H H H
119 N O H H CH 2F H H H
120 N O H H CH 2Br H H H
121 N O H H CH 2OCH 3 H H CH 2N(CH 3) 2
122 N O H Cl CH 2OCH 3 H H CH 2N(CH 3) 2
123 N O H CH 3 CH 2OCH 3 H H CH 2N(CH 3) 2
124 N O H H CH 2OCH 3 H H F
125 N O H CH 3 CH 2OCH 3 H H F
126 N O H CH 3 CH 2OCH 3 H CO 2CH 3 CH 2N(CH 3) 2
127 N O H H CH 2OCH 3 H H H
128 N O H H CH 2OCH 3 H H E
129 N O H H 3-CF 3-C 6H 4 H E H
130 N O H H 3-CH 3-C 6H 4 H COCH 3 H
131 N O H H 4-CH 3-C 6H 4 H H COCH 3
132 N O H Cl CH 2OC 2H 5 H H H
133 N O H H CH 2OC 2H 5 H H H
134 N O H H CH 2OC 2H 5 H H CH 3
135 N O H H 3-OCH 3-C 6H 4 H H CH 3
136 N O H CH 3 4-OCH 3-C 6H 4 H H H
137 N O H CH 3 2-OCH 3-C 6H 4 H H CH 3
138 N O H H CH 2OC 2H 5 H H Cl
139 N O H H CH 2OC 2H 5 H H E
140 N O H H M H E H
141 N O H H 3-CF 3-C 6H 4 H COCH 3 H
142 N O H H 3-CH 3-C 6H 4 H H COCH 3
143 N O H H 4-CH 3-C 6H 4 H H H
144 N O H H 2-Cl-C 6H 4 H H H
145 N O H H 3-Cl-C 6H 4 H H CH 3
146 N O H H CH 2OCH 2CF 3 H H CH 3
147 N O H CH 3 CH 2OCH 2CF 3 H H H
148 N O H CH 3 -CH 2OC 6H 5 H H CH 3
149 N O H H -CH 2OC 6H 5 H H H
150 N O H H CH 2OCH 2C 6H 5 H H E
151 N O H H CH 2OCH 2C 6H 5 H E H
152 N O H H 4-Cl-C 6H 4 H COCH 3 H
153 N NH H H CH 3 H H H 210-214
154 N NH H CH 3 CH 3 H H CH 3 178～180
155 N NH H H 2-Cl-C 6H 4 H H CH 3
156 N NH H CH 3 3-Cl-C 6H 4 H H H
157 N NH H CH 3 4-Cl-C 6H 4 H H CH 3
158 N NH H Cl CH 2Cl H H H
159 N NH H Cl CH 3 H H H
160 N NH H H 3-CF 3-C 6H 4 H E H
161 N NH H H 3-CH 3-C 6H 4 H COCH 3 H
162 N NH H H 4-CH 3-C 6H 4 H H COCH 3
163 N NH H H CH 2OCH 3 H H H
164 N NH H H 4-F-C 6H 4 H H H
165 N NH H H 2-F-C 6H 4 H H CH 3
166 N NH H H C 6H 3-3，5(Cl) 2 H H CH 3
167 N NH H CH 3 2-OCH 3-C 6H 4 H H H
168 N NH H CH 3 2-OCH 3-C 6H 4 H H CH 3
169 N NH H Cl CH 2OCH 3 H H H
170 N NH H H CH 2OCH 3 H H E
171 N NH H H 3，5(Cl) 2-C 6H 3 H E H
172 N NH H H 2，4(Cl) 2-C 6H 3 H H H
173 N NH H H 3，4(Cl) 2-C 6H 3 H H H
174 N NH H Cl CH 2OC 2H 5 H H H
175 N NH H H CH 2OC 2H 5 H H H
176 N NH H H CH 2OC 2H 5 H H CH 3
177 N NH H H CF 3 H H CH 3
178 N NH H CH 3 CF 3 H H H
179 N NH H CH 3 Cl H H CH 3
180 N NH H H Cl H H H
181 N NH H H CH 3 H H Cl
182 N NH H H C 6H 5 H H Cl
183 N NH H CH 3 CH 3 H H F
184 N NH H CH 3 CH 3 H H H
185 N NH H H CF 3 H H Cl
186 N NH H CH 3 4-F-C 6H 4 H H CH 3
187 N NH H H 2-F-C 6H 4 H E CO 2CH 3
188 N NH H H 2-Cl-C 6H 4 H COCH 3 CO 2CH 3
189 N NH H H 3-Cl-C 6H 4 H H CO 2CH 3
190 N NH H H 4-Cl-C 6H 4 H H CO 2CH 3
191 N NH H H CH 2Cl H CH 3 H
192 N NH H H CH 2Cl H CO 2C 2H 5 CF 3
193 N NH H H CH 2Cl H H CF 3
194 N NH H CH 3 M H CO 2C 2H 5 CF 3
195 N NH H CH 3 CH 2Cl H H CF 3
196 N NH H H CH 2Cl H H H
197 N NH H H CH 2Cl H H E
198 N NH H H CH 2Cl H E H
199 N NH H H CH 2Cl H COCH 3 H
200 N NH H CH 3 3，5-diCl-C 6H 3 H CO 2CH 3 H
201 CH O CH 3 H H H H H
202 CH O CH 3 H CH 3 H H H
203 CH O CH 3 H CH 3 H H CH 3
204 CH O CH 3 H C 6H 5 H H CH 3
205 CH O CH 3 CH 3 CH 3 H H H
206 CH O CH 3 CH 3 CH 3 H H CH 3
207 CH O CH 3 H CF 3 H H H
208 CH O CH 3 H CH 3 H H E
209 CH O CH 3 H CH 3 H E H
210 CH O CH 3 H CH 3 H COCH 3 H
211 CH O CH 3 H CH 3 H H COCH 3
212 CH O CH 3 H CH 2Cl H H H
213 CH O CH 3 Cl CH 2Cl H H H
214 CH O CH 3 H CH 2Cl H H CF 3
215 CH O CH 3 H CH 2Cl H H CH 3
216 CH O CH 3 CH 3 CH 2OCH 3 H H H
217 CH O CH 3 CH 3 CH 2OCH 3 H H CH 3
218 CH O CH 3 OCH 3 CH 2Cl H H H
219 CH O CH 3 H CH 2Cl H H E
220 CH O CH 3 H CH 2Cl H E H
221 CH O CH 3 H CH 2Cl H COCH 3 H
222 CH O CH 3 H CH 2Cl H H COCH3
223 CH O CH 3 H CH 2OCH 2CF 3 H H H
224 CH O CH 3 Cl CH 2OC 2H 5 H H H
225 CH O CH 3 Cl CH 2OCH 3 H H CH 3
226 CH O CH 3 H CH 2OCH 3 H H CH 3
227 CH O CH 3 CH 3 3-CF 3-C 6H 4 H H H
228 CH O CH 3 CH 3 3-CH 3-C 6H 4 H H CH 3
229 CH O CH 3 H 4-CH 3-C 6H 4 H H H
230 CH O CH 3 H 2-Cl-C 6H 4 H H E
231 CH O CH 3 H 3-Cl-C 6H 4 H E H
232 CH O CH 3 H CF 3 H COCH 3 H
233 CH O CH 3 Cl CH 2OCH 3 H H COCH 3
234 CH O CH 3 OCH 3 CH 2OC 2H 5 H H H
235 CH O CH 3 C 2H 5 CH 2OC 2H 5 H CH 3 H
236 CH O CH 3 H CH 2OC 2H 5 H H CH 3
237 CH O CH 3 Cl CH 2OC 2H 5 H CO 2C 2H 5 CH 3
238 CH O CH 3 CH 3 2-F-C 6H 4 H H H
239 CH O CH 3 CH 3 3-F-C 6H 4 H H CH 3
240 CH O CH 3 H 4-F-C 6H 4 H H H
241 CH O CH 3 H CH 2OC 2H 5 H H E
242 CH O CH 3 H CH 2OC 2H 5 H E H
243 CH O CH 3 H CH 2OC 2H 5 H COCH 3 H
244 CH O CH 3 H CH 2OC 2H 5 H H COCH 3
245 CH O CH 3 H CH 2OCH 2CF 3 H H H
246 CH O CH 3 Cl CH 2OCH 2CF 3 H H H
247 CH O CH 3 H CF 3 H H CH 3
248 CH O CH 3 H CH 2OCH 2CF 3 H H CH 3
249 CH O CH 3 CH 3 CH 2OCH 2CF 3 H H H
250 CH O CH 3 CH 3 -CH 2OPh H H CH 3
251 CH O CH 3 H -CH 2OPh H H H
252 CH O CH 3 H CH 2OCH 2Ph H H E
253 CH O CH 3 H CH 2OCH 2Ph H E H
254 CH O CH 3 H 4-Cl-C 6H 5 H COCH 3 H
255 CH O CH 3 H 4-Cl-C 6H 5 H H COCH 3
256 CH O CH 3 H M H CO 2C 2H 5 H
257 CH O CH 3 H M H H H
258 CH O CH 3 Cl M H H CH 3
259 CH O CH 3 H M H H CH 3
260 CH O CH 3 CH 3 M H H H
261 CH NH CH 3 Cl H H H H
262 CH NH CH 3 Cl CH 3 H H H
263 CH NH CH 3 H CH 3 H H CH 3
264 CH NH CH 3 H C 6H 5 H H CH 3
265 CH NH CH 3 CH 3 CH 3 H H H
266 CH NH CH 3 CH 3 CH 3 H H CH 3
267 CH NH CH 3 OCH 3 CF 3 H H H
268 CH NH CH 3 OCH 3 CH 3 H H E
269 CH NH CH 3 H CH 3 H E H
270 CH NH CH 3 H CH 3 H COCH 3 H
271 CH NH CH 3 H CH 3 H H COCH 3
272 CH NH CH 3 H CH 2Cl H H H
273 CH NH CH 3 H M H H H
274 CH NH CH 3 H CH 2Cl H H CH 3
275 CH NH CH 3 H CF 3 H H CH 3
276 CH NH CH 3 CH 3 CH 2Cl H H H
277 CH NH CH 3 CH 3 CH 2Cl H H CH 3
278 CH NH CH 3 Cl CH 2Cl H H H
279 CH NH CH 3 H M H H E
280 CH NH CH 3 H M H E H
281 CH NH CH 3 H M H COCH 3 H
282 CH NH CH 3 H M H H COCH 3
283 CH NH CH 3 Cl CH 2OCH 3 H H H
284 CH NH CH 3 H 4-C 6H 5Cl H H H
285 CH NH CH 3 H 4-C 6H 5Cl H H CH 3
286 CH NH CH 3 H CH 2OCH 3 H H CH 3
287 CH NH CH 3 CH 3 CH 2OCH 3 H H H
288 CH NH CH 3 CH 3 CH 2OCH 3 H H CH 3
289 CH NH CH 3 H CH 2OCH 3 H H H
290 CH NH CH 3 H CH 2OCH 3 H H E
291 CH NH CH 3 H CH 2OCH 2CF 3 H E H
292 CH NH CH 3 H CH 2OCH 2CF 3 H COCH 3 H
293 CH NH CH 3 H CH 2OCH 2CF 3 H H COCH 3
294 CH NH CH 3 Cl CH 2OC 2H 5 H H H
295 CH NH CH 3 H CH 2OC 2H 5 H H H
296 CH NH CH 3 H CH 2OC 2H 5 H H CH 3
297 CH NH CH 3 H CF 3 H H CH 3
298 CH NH CH 3 CH 3 CF 3 H H H
299 CH NH CH 3 CH 3 Cl H H CH 3
300 CH NH CH 3 H Cl H H H
301 N O CH 3 H CH 3 H H H
302 N O CH 3 H C 6H 5 H H Cl
303 N O CH 3 CH 3 CH 3 H H H
304 N O CH 3 CH 3 CH 3 H H H
305 N O CH 3 H CF 3 H H Cl
306 N O CH 3 CH 3 CH 3 H H CH 3
307 N O CH 3 H CH 3 H E CO 2CH 3
308 N O CH 3 H CH 3 H COCH 3 CO 2CH 3
309 N O CH 3 H CH 3 H H CO 2CH 3
310 N O CH 3 H CH 2Cl H H CO 2CH 3
311 N O CH 3 H H H H H
312 N O CH 3 H CH 2Cl H H CF 3
313 N O CH 3 H 3-CF 3-C 6H 4 H H CF 3
314 N O CH 3 CH 3 3-CH 3-C 6H 4 H H CF 3
315 N O CH 3 CH 3 4-CH 3-C 6H 4 H H CF 3
316 N O CH 3 H CH 2Cl H H H
317 N O CH 3 H CH 2Cl H H E
318 N O CH 3 H CH 2Cl H E H
319 N O CH 3 H CH 2Cl H COCH 3 H
320 N O CH 3 H CH 2Cl H H COCH3
321 N O CH 3 H CH 2OCH 3 H H CH 2N(CH 3) 2
322 N O CH 3 Cl CH 2OCH 3 H H CH 2N(CH 3) 2
323 N O CH 3 CH 3 CH 2OCH 3 H H CH 2N(CH 3) 2
324 N O CH 3 H CH 2OCH 3 H H F
325 N O CH 3 CH 3 CH 2OCH 3 H H F
326 N O CH 3 CH 3 CH 2OCH 3 H CO 2CH 3 CH 2N(CH 3) 2
327 N O CH 3 H CH 2OCH 3 H H H
328 N O CH 3 H CH 2OCH 3 H H E
329 N O CH 3 H 3-CF 3-C 6H 4 H E H
330 N O CH 3 H 3-CH 3-C 6H 4 H COCH 3 H
331 N O CH 3 H 4-CH 3-C 6H 4 H H COCH 3
332 N O CH 3 Cl CH 2OC 2H 5 H H H
333 N O CH 3 H CH 2OC 2H 5 H H H
334 N O CH 3 H CH 2OC 2H 5 H H CH 3
335 N O CH 3 H 3-OCH 3-C 6H 4 H H CH 3
336 N O CH 3 CH 3 4-OCH 3-C 6H 4 H H H
337 N O CH 3 CH 3 2-OCH 3-C 6H 4 H H CH 3
338 N O CH 3 H CH 2OC 2H 5 H H Cl
339 N O CH 3 H CH 2OC 2H 5 H H E
340 N O CH 3 H M H E H
341 N O CH 3 H 3-CF 3-C 6H 4 H COCH 3 H
342 N O CH 3 H 3-CH 3-C 6H 4 H H COCH 3
343 N O CH 3 H 4-CH 3-C 6H 4 H H H
344 N O CH 3 H 2-Cl-C 6H 4 H H H
345 N O CH 3 H 3-Cl-C 6H 4 H H CH 3
346 N O CH 3 H CH 2OCH 2CF 3 H H CH 3
347 N O CH 3 CH 3 CH 2OCH 2CF 3 H H H
348 N O CH 3 CH 3 -CH 2OPh H H CH 3
349 N O CH 3 H -CH 2OPh H H H
350 N O CH 3 H CH 2OCH 2Ph H H E
351 N O CH 3 H CH 2OCH 2Ph H E H
352 N O CH 3 H 4-Cl-C 6H 4 H COCH 3 H
353 N NH CH 3 H CH 3 H H H
354 N NH CH 3 CH 3 CH 3 H H CH 3
355 N NH CH 3 H 2-Cl-C 6H 4 H H CH 3
356 N NH CH 3 CH 3 3-Cl-C 6H 4 H H H
357 N NH CH 3 CH 3 4-Cl-C 6H 4 H H CH 3
358 N NH CH 3 H CH 2Cl H H H
359 N NH CH 3 H M H H E
360 N NH CH 3 H 3-CF 3-C 6H 4 H E H
361 N NH CH 3 H 3-CH 3-C 6H 4 H COCH 3 H
362 N NH CH 3 H 4-CH 3-C 6H 4 H H COCH 3
363 N NH CH 3 H CH 2OCH 3 H H H
364 N NH CH 3 H 4-F-C 6H 4 H H H
365 N NH CH 3 H 2-F-C 6H 4 H H CH 3
366 N NH CH 3 H C 6H 3-3，5(Cl) 2 H H CH 3
367 N NH CH 3 CH 3 2-OCH 3-C 6H 4 H H H
368 N NH CH 3 CH 3 2-OCH 3-C 6H 4 H H CH 3
369 N NH CH 3 Cl CH 2OCH 3 H H H
370 N NH CH 3 H CH 2OCH 3 H H E
371 N NH CH 3 H C 6H 3-3，5(Cl) 2 H E H
372 N NH CH 3 H CH 2OCH 2CF 3 H COCH 3 H
373 N NH CH 3 H CH 2OCH 2CF 3 H H COCH 3
374 N NH CH 3 Cl CH 2OC 2H 5 H H H
375 N NH CH 3 H CH 2OC 2H 5 H H H
376 N NH CH 3 H CH 2OC 2H 5 H H CH 3
377 N NH CH 3 H CF 3 H H CH 3
378 N NH CH 3 CH 3 CF 3 H H H
379 N NH CH 3 CH 3 Cl H H CH 3
380 N NH CH 3 H Cl H H H
381 N NH CH 3 H CH 3 H H Cl
382 N NH CH 3 H C 6H 5 H H Cl
383 N NH CH 3 CH 3 CH 3 H H F
384 N NH CH 3 CH 3 CH 3 H H H
385 N NH CH 3 H CF 3 H H Cl
386 N NH CH 3 CH 3 4-F-C 6H 4 H H CH 3
387 N NH CH 3 H 2-F-C 6H 4 H E CO 2CH 3
388 N NH CH 3 H 2-Cl-C 6H 4 H COCH 3 CO 2CH 3
389 N NH CH 3 H 3-Cl-C 6H 4 H H CO 2CH 3
390 N NH CH 3 H 4-Cl-C 6H 4 H H CO 2CH 3
391 N NH CH 3 H CH 2Cl H CH 3 H
392 N NH CH 3 H CH 2Cl H CO 2C 2H 5 CF 3
393 N NH CH 3 H CH 2Cl H H CF 3
394 N NH CH 3 CH 3 M H CO 2C 2H 5 CF 3
395 N NH CH 3 CH 3 CH 2Cl H H CF 3
396 N NH CH 3 H CH 2Cl H H H
397 N NH CH 3 H CH 2Cl H H E
398 N NH CH 3 H CH 2Cl H E H
399 N NH CH 3 H CH 2Cl H COCH 3 H
400 N NH CH 3 CH 3 3，5-diCl-C 6H 3 H CO 2CH 3 H
*The numeral fusing point, unit ℃.
The nuclear magnetic data of part of compounds ( 1HNMR, 300MHz, interior mark TMS, solvent C DCl 3) as follows:
Compound 1: δ ppm 3.69 (3H, s), 3.88 (3H, s), 5.04 (2H, s), 6.19-6.23 (1H, d), 6.77 (1H, s), 6.83-6.87 (1H, d), 7.18-7.20 (1H, m), 7.26-7.34 (4H, m), 7.48-7.64 (2H, m).
Compound 2: δ ppm 2.38 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.11 (1H, s), 6.77 (1H, s), 6.85-6.89 (1H, d), 7.17-7.20 (1H, m), 7.32-7.35 (2H, m), 7.49-7.52 (2H, m), 7.64 (1H, s).
Compound 3: δ ppm 2.36 (3H, s), 2.37 (3H, s), 3.72 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.13 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.34-7.36 (3H, m), 7.50-7.52 (1H, and m) 7.61 (1H, s).
Compound 4: δ ppm 2.41 (3H, s), 3.69 (3H, s), 3.81 (3H, s), 5.08 (2H, s), 6.20 (1H, s), 6.68-6.71 (1H, d), 7.18-7.21 (4H, m), 7.32-7.50 (5H, m), 7.59 (1H, s), 7.92 (1H, m).
Compound 5: δ ppm 2.17 (3H, s), 2.35 (3H, s), 3.73 (3H, s), 3.88 (3H, s), 5.02 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.31-7.34 (3H, m), 7.45-7.47 (2H, d), 7.62 (1H, s).
Compound 6: δ ppm 2.32 (3H, s), 2.31-2.36 (6H, d), 3.69 (3H, s), 3.84 (3H, s), 5.07 (2H, s), 6.74-6.77 (1H, d), 7.17-7.20 (1H, m), 7.31-7.36 (3H, m), 7.51-7.54 (1H, m), 7.61 (1H, s).
Compound 12: δ ppm 2.53 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, s), 6.83-6.85 (1H, d), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.47-7.50 (2H, d), 7.64 (1H, s).
Compound 17: δ ppm 1.25-1.32 (3H, m), 2.36 (3H, s), 2.74-2.76 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.15 (1H, s), 6.75-6.78 (1H, d), 7.18-7.21 (1H, m), 7.33-7.38 (3H, m), 7.50-7.54 (1H, m), 7.61 (1H, s).
Compound 24: δ ppm 3.72 (3H, s), 3.92 (3H, s), 5.10 (2H, s), 6.78 (1H, s), 6.94-7.21 (1H, d), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.36-7.45 (2H, m), 7.66 (1H, s), 8.13 (1H, s).
Compound 25: δ ppm 2.36 (3H, d), 2.62 (3H, d), 3.71 (3H, s), 3.84 (3H, s), 5.09 (2H, s), 6.82 (1H, d), 7.19-7.21 (1H, m), 7.33-7.35 (3H, m), 7.36-7.37 (1H, m), 7.61 (1H, s).
Compound 26: δ ppm 1.25-1.30 (6H, m), 3.20-3.23 (1H, m), 3.74 (3H, s), 3.91 (3H, s), 5.04 (2H, s), 6.15 (1H, s), 6.790-6.799 (1H, d), 6.80-6.90 (1H, m), 7.18-7.23 (1H, m), 7.32-7.37 (2H, m), 7.48-7.57 (2H, m), 7.64 (1H, s).
Compound 27: δ ppm 0.95-1.00 (3H, t), 1.58 (2H, m), 2.36 (3H, s), 2.58 (2H, t), 3.73 (3H, s), 3.89 (3H, s), 5.02 (2H, s), 6.75 (1H, d), 6.84-6.88 (1H, dd), 7.18 (1H, m), 7.31-7.34 (1H, m), 7.47-7.51 (2H, m), 7.63 (1H, s).
Compound 32: δ ppm 3.73 (3H, s), 3.90 (3H, s), 5.05 (2H, s), 6.75-6.78 (1H, dd), and 6.84-6.85 (1H, d), 6.94-6.98 (1H, d), 7.19-7.21 (1H, m), 7.30-7.35 (4H, m), 7.53-7.55 (4H, m), 7.65 (1H, s).
Compound 33: δ ppm 1.27-1.32 (3H, m), 2.74-2.77 (2H, m), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.13 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.18-7.21 (1H, m), 7.32-7.35 (2H, m), 7.48-7.52 (2H, m), 7.64 (1H, s).
Compound 34: δ ppm 0.90-1.03 (3H, m), 1.67-1.72 (2H, m), 2.65-2.70 (2H, m), 3.73 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.10 (1H, s), 6.78-6.79 (1H, d), 6.85-6.89 (1H, m), 7.19-7.21 (1H, m), 7.33-7.35 (2H, m), 7.47-7.51 (2H, m), 7.64 (1H, s).
Compound 35: δ ppm 1.00-1.25 (3H, m), 1.69-1.72 (2H, m), 2.36 (3H, s), 2.65-2.70 (2H, m), 3.71 (3H, s), 3.84 (3H, s), 5.08 (2H, s), 6.12 (1H, s), 6.75-6.78 (1H, d), 7.21-7.26 (1H, m), 7.33-7.38 (3H, m), 7.50-7.53 (1H, m), 7.61 (1H, s).
Compound 36: δ ppm 0.97 (3H, t), 1.66 (2H, m), 2.67 (3H, s), 3.74 (3H, s), 3.89 (3H, s), 5.04 (2H, s), 6.78 (1H, d), 6.85-6.88 (1H, dd), 7.22 (1H, m), 7.33-7.35 (2H, m), 7.46-7.49 (2H, m), 7.64 (1H, s).
Compound 52: δ ppm 3.74 (3H, s), 3.90 (3H, s), 5.06 (2H, s), 6.20 (1H, s), and 6.80-6.86 (1H, m), 7.18-7.22 (1H, m), 7.32-7.37 (4H, m), 7.41-7.44 (2H, m), 7.50-7.52 (4H, m), 7.65 (1H, s).
Compound 100: δ ppm 2.54 (3H, s), 3.87 (3H, s), 4.04 (3H, s), 5.02 (2H, s), 6.81-6.85 (1H, s), 7.26 (1H, d), 7.43-7.52 (5H, m).
Compound 101: δ ppm 2.39 (3H, s), 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.80-6.86 (2H, m), 7.23-7.26 (1H, m), 7.43-7.49 (4H, m).
Compound 102: δ ppm 2.32 (3H, s), 2.37 (3H, s), 3.84 (3H, s), 4.03 (3H, s), 5.05 (2H, s), 6.13 (1H, s), 6.76-6.79 (1H, d), 7.26 (1H, d), 7.34-7.43 (3H, m), 7.45-7.46 (1H, d).
Compound 103: δ ppm 2.18 (3H, s), 2.37 (3H, s), 3.91 (3H, s), 3.98 (3H, s), 5.35 (2H, s), 6.85 (1H, s), 6.86-6.88 (1H, d), 7.26-7.40 (3H, m), 7.49-7.52 (1H, d), 7.62-7.65 (1H, d).
Compound 104: δ ppm 2.17 (3H, s), 2.35 (3H, s), 3.86 (3H, s), 4.04 (3H, s), 5.00 (2H, s), 6.78-6.85 (2H, m), 7.20-7.25 (1H, d), 7.40-7.61 (4H, m).
Compound 109: δ ppm 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), and 6.82-6.86 (3H, m), 7.20-7.23 (1H, m), 7.34-7.37 (1H, d), 7.39-7.45 (2H, m), 7.50-7.53 (1H, m), 7.61-7.64 (1H, d).
Compound 111: δ ppm 3.87 (3H, s), 4.05 (3H, s), 5.02 (2H, s), 6.23-6.26 (1H, d), 6.79-6.85 (2H, m), 7.21 (1H, d), 7.34-7.37 (1H, d), 7.41-7.45 (2H, m), 7.47-7.53 (1H, m), 7.61-7.64 (1H, d).
Compound 153: δ ppm 2.38 (3H, s), 2.91-2.93 (3H, d), 3.97 (3H, s), 5.02 (2H, s), 6.13 (1H, s), 6.82-6.87 (3H, m), 7.23 (1H, d), 7.39-7.50 (4H, m).
The present invention also comprises the preparation method of general formula (I) compound: can prepare by the step shown in the reaction formula 1.R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8, A, B definition as above, Z is a leavings group, as halogen (chlorine, bromine or iodine).
Reaction formula 1:
Figure C20031010507900171
General formula (I) compound can prepare like this: in appropriate solvent, form salt with the grevillone compounds shown in the suitable alkaline purification general formula (III), the compound that adds formula (II) then behind reaction certain hour under the suitable temperature, handles promptly getting the purpose product.
The optional tetrahydrofuran (THF) freely of appropriate solvent, acetonitrile, toluene, dimethylbenzene, benzene, N, N dimethyl formamide, methyl-sulphoxide, acetone or butanone etc.
The optional potassium hydroxide freely of suitable alkali, sodium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, triethylamine, pyridine or sodium hydride etc.
Suitable temperature refers to room temperature to the solvent boiling point temperature, is generally 20～100 ℃.
Reaction times is 30 minutes to 20 hours, common 1～10 hour.
Compound shown in the general formula (II) can be made by currently known methods, sees USP4723034, USP5554578.Grevillone compounds shown in the general formula (III) can be by R 5COCHR 4CO 2CH 3(C 2H 5) make with the Resorcinol that replaces reaction in suitable condensing agent (as the vitriol oil, trifluoroacetic acid).
Logical formula V and compound (VII) can be respectively by general formula (IV) and (VI) react with aqueous methylamine solution and acquisition at an easy rate:
Figure C20031010507900181
A＝N，B＝O(IV)； A＝N，B＝NH(V)；
A＝CH，B＝O(VI)； A＝CH，B＝NH(VII)。
Compound of the present invention has excellent insecticidal activity, can be used for preventing and treating various pest on crop.For example can be used for preventing and treating mythimna separata, small cabbage moth, black peach aphid, carmine spider mite, Tetranychus urticae, ladybug, evil mite and culex pipiens pollens.Especially ladybug and culex pipiens pollens there are special efficacy, are particularly suitable for integrated control insect.
Compound of the present invention has excellent fungicidal activity simultaneously, they have systemic activity and can be used as the blade face and soil fungicides, can be applicable to the disease on the various crops of control, be particularly suitable for preventing and treating the following plants disease: downy mildew of garpe, rice sheath blight disease, rice blast, early blight of tomato, tomato late blight, wheat rust, speckled leaf blotch, wheat powdery mildew, powdery mildew of cucumber, cucumber downy mildew, gray mold of cucumber etc.
The present invention also provides a kind of desinsection, fungicidal composition, contains the compound and the steric isomer thereof of general formula (I) in the said composition, and the weight percentage of active ingredient is 0.1-99%.
The present invention also provides preparation of compositions method as defined above: the compound of general formula (I) is mixed with carrier.This composition can contain the mixture of simplification compound of the present invention or several compounds.
Carrier system in the present composition satisfies the material of following condition: being convenient to be applied to pending site after it and activeconstituents are prepared, for example can be plant, seed or soil; Perhaps help storing, transport or operation.Carrier can be solid or liquid, comprises the material that is generally gas but has been compressed into liquid, and used carrier all can use in preparation desinsection, fungicidal composition usually.
Suitable solid carrier comprises natural and synthetic clay and silicate, for example diatomite, talcum, attapulgite, pure aluminium silicate (kaolin), montmorillonite and mica; Lime carbonate; Calcium sulfate; Ammonium sulfate; Synthetic silicon oxide and synthetic calcium silicate or pure aluminium silicate; Element such as carbon and sulphur; Natural and synthetic resin such as coumarone resin, polyvinyl chloride and styrene polymer and multipolymer; Solid polystream phenol; Pitch; Wax such as beeswax, paraffin.
Suitable liquid vehicle comprises water; Alcohol is as Virahol and ethanol; Ketone such as acetone, methyl ethyl ketone, methyl isopropyl Ketone, cyclohexyl ketone; Ether; Aromatic hydrocarbons such as benzene,toluene,xylene; Petroleum fractions such as kerosene and mineral oil; Hydrochloric ether such as tetracol phenixin, tetrachloroethylene and trieline.Usually, these mixtures of liquids also are suitable.
Desinsection, fungicidal composition are processed into the form of enriched material usually and are used for transportation with this, by the user it are diluted before using.Having of a spot of supporting surfactant helps dilution.Like this, according to having preferably tensio-active agent of a kind of carrier in the composition of the present invention at least.For example composition can contain at least two kinds of carriers, and wherein at least a is tensio-active agent.
Tensio-active agent can be emulsifying agent, dispersion agent or wetting agent; It can be non-ionic or the ionic tensio-active agent.The example of suitable tensio-active agent comprises the sodium salt or the calcium salt of polyacrylic acid and lignosulfonic acid; Contain the lipid acid of at least 12 carbon atoms or the condenses of aliphatic amide or acid amides and oxyethane and/or propylene oxide in the molecule.The condenses of glycol, sorbyl alcohol, sucrose or pentaerythritol fatty ester and these esters and oxyethane and/or propylene oxide; Fatty Alcohol(C12-C14 and C12-C18) or alkylphenol such as paraoctyl phenol or to the condenses of octyl group cresylol and oxyethane and/or propylene oxide; The vitriol of these condensation products and sulfonate; In molecule, contain the sulfuric acid of 10 carbon atoms or the basic metal or the alkaline earth salt of sulphonate at least, particular certain cancers, sulfuric acid laurate sodium for example, the secondary alkyl ester sodium of sulfuric acid, the sulfonated castor oil sodium salt, alkyl aryl sulfonic acid ester sodium is as pelopon A.
The example of composition of the present invention is wettable powder, pulvis, granule and solution, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 25,50 or 75% weight activeconstituents usually, and usually except that solid inert carrier, also contains the dispersion agent of 3-10% weight, and if needs to add stablizer and/or other additive such as the permeate agent or the tackiness agent of 0-10% weight.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but do not have dispersion agent usually, further with the solid carrier dilution, is contained the composition of 0.5-10% weight active ingredient usually again.Granula is prepared into usually has 10 to 100 order (1.676-0.152mm) sizes, and available agglomerating or implantttion technique preparation.Usually granula contains the activeconstituents of 0.5-75% weight and 0-10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.So-called " dry powder can flow " is by the relatively little granulometric composition with relative high density activeconstituents.Outside but emulsion concentrate desolventizes, when needs, contain cosolvent usually, 1-50%W/V activeconstituents, other additives of 2-20%W/V emulsifying agent and 0-20%W/V such as stablizer, permeate agent and corrosion inhibitor.The suspension enriching agent contains the activeconstituents of 10-75% weight, the dispersion agent of 0.5-15% weight, other additive such as defoamer, corrosion inhibitor, stablizer, permeate agent and the tackiness agent of 0.1-10% weight usually.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list the scope of the invention in.Said emulsion can have water-in-oil or two types of oil-in-water.
By in composition, adding other one or more sterilant, make it have the more activity of wide spectrum than independent general formula (I) compound.In addition, but the fungicidal activity of other sterilant mutual-through type (I) compounds has synergism.Also general formula (I) compound and other sterilants can be used with, or use with another kind of sterilant and other sterilants simultaneously.
Embodiment
Below further specify the present invention with concrete example.
Synthetic embodiment
Example 1: the preparation method of compound 1
At room temperature, the sodium hydride of 0.84 gram 60% is added in the reaction flask, after petroleum ether, to wherein adding 30 milliliters of exsiccant N, N dimethyl formamide, stirring reaction half an hour, to wherein adding 1.7 gram umbelliferones, continue to be stirred to no gas and emit, add 3 gram (E)-2-[2-(brooethyl) phenyl]-the 3-methoxy-methyl acrylate, continue to stir 3 hours.Reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, with saturated common salt washing 3 times, drying is filtered, and concentrating under reduced pressure gets oily liquids 5 grams.Column chromatography obtains title compound 2.8 grams, is pale red yellow oil, yield 76.5%.
Example 2: the preparation of compound 2
At room temperature, the sodium hydride of 0.45 gram 60% is added in the reaction flask, after petroleum ether, to wherein adding 20 milliliters of exsiccant N, N dimethyl formamide, stirring reaction half an hour, to wherein adding 1.0 gram 7-hydroxy-4-methylcoumarins, continue to be stirred to no gas and emit, add 1.66 gram (E)-2-[2-(brooethyl) phenyl]-the 3-methoxy-methyl acrylate, continue to stir 3 hours.Reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, with saturated common salt washing 3 times, drying is filtered, concentrating under reduced pressure, getting yellow solid is thick product.Mixed solution (1: 2) column chromatography with ethyl acetate and sherwood oil obtains title compound 1.73 grams, fusing point 140-143 ℃.Yield 80%.
Example 3: the preparation of compound 101
At room temperature, to contain 1.2 gram Anhydrous potassium carbonates, 1.0 gram 7-hydroxy-4-methylcoumarins, 1.70 gram 2-brooethyl-α-(methoxy imino) methyl phenylacetates in the mixed solution reflux stirring reaction of 20 milliliters of butanone 5 hours, reaction mixture is poured in the frozen water, ethyl acetate extraction 3 times, combining extraction liquid, saturated common salt washing 3 times, dry, filter, concentrating under reduced pressure, getting yellow solid is thick product.Mixed solution (1: 2) column chromatography with ethyl acetate and sherwood oil obtains title compound 1.77 grams, fusing point 150-152 ℃.Yield 83%.
Example 4: the preparation of compound 153
With 0.27 methylamine stirred overnight at room temperature in 30 ml methanol of digesting compound 101 and twice as high molar ratio, concentrate the back with ethyl acetate extraction 2 times, the extract of merging washes with water 3 times, with saturated common salt washing 2 times, drying is filtered again, concentrate, get title compound 0.24 gram, fusing point 210-214 ℃.Yield 89%.
Other compounds are synthetic with reference to aforesaid method.
Example of formulations
Example 5 60% wettable powders
Compound 6 60% (weight)
Dodecyl sodium naphthalene sulfonate 2% (weight)
Sodium lignosulfonate 9% (weight)
Kaolin 31% (weight)
Each component (being solid) mixes, and pulverizes in pulverizer, reaches standard up to particle.
Example 6 35% missible oil
Compound 1 35% (weight)
Phosphorous acid 10% (weight)
Ethoxylated glycerol three acid esters 15% (weight)
Pimelinketone 40% (weight)
Phosphorous acid is dissolved in the pimelinketone, adds compound 1 and ethoxylated glycerol three acid esters then, obtains transparent solution.
Example 7 30% aq suspensions
Compound 25 30% (weight)
Dodecyl sodium naphthalene sulfonate 4% (weight)
Hemicellulose 2% (weight)
Propylene oxide 8% (weight)
Water 56% (weight)
Compound 25 is pulverized in (1mm pearl) in ball mill with 80% water and dodecyl sodium naphthalene sulfonate.Other components dissolved stirs other component of adding then in remaining water.
Example 8 25% suspension-emulsion enriched materials
Compound 12 25% (weight)
Dodecyl alcohol polyoxyethylene glycol phosphoric acid ester (emulsifying agent 1) 4% (weight)
Oxyethyl group tri-glyceride (emulsifying agent 2) 2% (weight)
Calcium dodecylbenzene sulphonate (emulsifying agent 3) 1.5% (weight)
The epoxy first and second alkane epoxy propane copolymers (dispersion agent) 2.5% (weight)
Pimelinketone (solvent 1) 30% (weight)
Alkylaryl cut (boiling point＞200 ℃) (solvent 2) 35% (weight)
Compound 12 is dissolved in 80% the solvent, adds emulsifying agent and dispersion agent then, and mixture is thoroughly stirred.Mixture is pulverized in ball mill (1mm pearl), adds remaining solvent then.
Biological activity determination
Example 9 fungicidal activities are measured
With The compounds of this invention the various fungus diseases of plant are tested.The program of test is as follows:
Plant is tried material to carry out potted plant.The former medicinal small amount of N of testing compound, the dinethylformamide dissolving is diluted with water to required concentration.Spray pesticide carries out the disease inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the fixed temperature and humidity incubator, makes to infect and continue, wait to contrast abundant morbidity back (being generally week age) and carry out assessment surveys.Part of compounds and document JP 04-182461 report compound JP51 control cucumber downy mildew specific activity the results are shown in Table 2.
The partial test result is as follows:
During 200ppm, to the cucumber downy mildew preventive effect be 100% compound 1,2,4,5,6,12,25,26,33,34,35,52,109 etc. are arranged; Preventive effect greater than 95% compound 3,24,36,153 etc. are arranged.
During 200ppm, to the gray mold of cucumber preventive effect be 100% compound 2,6,100 etc. are arranged; Preventive effect greater than 75% compound 6,101,102,103,106 etc. are arranged.
During 200ppm, to the downy mildew of garpe preventive effect be 100% compound 6,7,10 etc. are arranged; Preventive effect greater than 85% compound 8,106,154 etc. are arranged.
During 200ppm, to the rice sheath blight disease preventive effect greater than 85% compound 3,101 etc. arranged.
During 200ppm, to the rice blast preventive effect greater than 85% compound 6,8,10 etc. are arranged.
During 200ppm, to the wheat powdery mildew preventive effect greater than 70% compound 9,101,111 etc. are arranged.
During 200ppm, to the sick preventive effect of wheat rust be 100% compound 6 etc. arranged; Preventive effect greater than 95% compound 7,10 etc. arranged; Preventive effect greater than 75% compound 8,154 etc. arranged.
During 200ppm, to the speckled leaf blotch preventive effect greater than 90% compound 6 etc. arranged; Preventive effect greater than 80% compound 7,8,9,10,11,154 etc. are arranged.
During 200ppm, to the early blight of tomato preventive effect be 100% compound 6,7 etc. arranged; Preventive effect greater than 90% compound 8,10 etc. arranged; Preventive effect greater than 75% compound 11 etc. arranged.
During 200ppm, to the tomato late blight preventive effect greater than 95% compound 6 etc. arranged; Preventive effect greater than 75% compound 10 etc. arranged.
During 200ppm, to the corn southern leaf blight preventive effect greater than 95% compound 5,6 etc. arranged.
The active comparison test (50ppm) of table 2 control cucumber downy mildew
Compound 1 2 5 6 12 26 52 JP51
Preventive effect (%) 100 100 100 100 100 100 100 20
Biological activity determination
Example 10 pesticide and miticide actilities are measured
Get the third-instar larvae of some amount and put into Breeding container, raise with leaf of Semen Maydis through drug treating.Application method is the baud spraying.Spray value is 1mL, and spray pressure is 13.5 pounds/square inch.
Investigation and result's statistics:
When liquor strength was 10ppm, compound 2,5,6 etc. were to reaching 100% for examination target culex pipiens pollens mortality ratio.
When liquor strength is 600ppm, compound 5,6 also to mythimna separata, small cabbage moth, black peach aphid also show suitable activity, greater than 50%.
When liquor strength was 300ppm, 7,9,10 pairs of compounds supplied examination target Mexico ladybug mortality ratio to reach 100%; Compound 7 also shows suitable activity to Tetranychus urticae, greater than 50%.

Claims (8)

1, Benzofurantone compound and steric isomer thereof, shown in general formula (I):
In the formula: A is selected from CH or N; B is selected from O, S or NR 9R 9Be selected from hydrogen or C 1-C 12Alkyl; R 1, R 2Be selected from hydrogen, C respectively 1-C 12Alkyl or halo C 1-C 12Alkyl; R 3Be selected from hydrogen, C 1-C 12Alkyl, halo C 1-C 12Alkyl or C 1-C 12Alkoxyl group; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 12Alkyl, C 2-C 12Thiazolinyl, C 2-C 12Alkynyl, C 1-C 12Haloalkyl, C 1-C 12Alkoxyl group, C 1-C 12Alkylthio, C 1-C 12Alkane alkylsulfonyl, C 1-C 12Alkyl-carbonyl, C 1-C 12Alkoxy C 1-C 12Alkyl, C 1-C 12Alkoxy carbonyl, C 1-C 12Alkoxy carbonyl C 1-C 12Alkyl, C 1-C 12Halogenated alkoxy C 1-C 12Alkyl, C 1-C 2Alkylamino radical C 1-C 12Alkyl, aryloxy, fragrant C 1-C 12Alkyl oxy, aryl or contain aryl, heteroaryl, the aryl C of alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro substituent 1-C 12Alkyl, heteroaryl C 1-C 12Alkyl, heteroaryl C 1-C 12The group that alkoxyl group and following general formula are represented:
Figure C2003101050790002C2
Wherein: R 10, R 11Be selected from hydrogen, alkyl, aryl or aryl C respectively 1-C 12Alkyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NR 9
2, compound according to claim 1 is characterized in that: A is selected from CH or N in the general formula (I); B is selected from O, S or NR 9R 9Be hydrogen or C 1-C 6Alkyl; R 1, R 2Be selected from hydrogen, C respectively 1-C 6Alkyl or halo C 1-C 6Alkyl; R 3Be selected from hydrogen, C 1-C 6Alkyl or halo C 1-C 6Alkyl, C 1-C 6Alkoxyl group; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6Alkoxy carbonyl C 1-C 6Alkyl, C 1-C 6Halogenated alkoxy C 1-C 6Alkyl, C 1-C 2Alkylamino radical C 1-C 6Alkyl, aryloxy, fragrant C 1-C 6Alkyl oxy, aryl or contain aryl, heteroaryl, the aryl C of alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro substituent 1-C 6Alkyl, heteroaryl C 1-C 6Alkyl, heteroaryl C 1-C 6The group that alkoxyl group and following general formula are represented:
Wherein: R 10, R 11Be selected from hydrogen, alkyl, aryl, aryl C respectively 1-C 6Alkyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NR 9
3, compound according to claim 2 is characterized in that: A is selected from CH or N in the general formula (I); B is selected from O or NH; R 1, R 2Be selected from methyl respectively; R 3Be selected from hydrogen or methyl; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, halogen, cyano group, nitro, C respectively 1-C 6Alkyl, C 2-C 6Thiazolinyl, C 2-C 6Alkynyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6Alkane alkylsulfonyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxy C 1-C 6Alkyl, C 1-C 6Alkoxy carbonyl, C 1-C 6Alkoxy carbonyl C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, C 1-C 2Alkylamino radical C 1-C 3Alkyl, phenoxy group, benzyloxy, phenyl or contain phenyl, the benzyl of alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro substituent, and the group represented of following general formula:
Figure C2003101050790003C1
Wherein: R 10, R 11Be selected from hydrogen or alkyl respectively; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NH.
4, compound according to claim 3 is characterized in that: A is selected from CH or N in the general formula (I); B is selected from O or NH; R 1, R 2Be selected from methyl; R 3Be selected from hydrogen or methyl; R 4, R 5, R 6, R 7, R 8Can be identical or different, be selected from hydrogen, chlorine, bromine, fluorine, cyano group, C respectively 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkyl-carbonyl, C 1-C 6Alkoxyl group, C 1-C 6Alkoxy C 1-C 3Alkyl, C 1-C 3Halogenated alkoxy C 1-C 3Alkyl, C 1-C 2Alkylamino radical C 1-C 3Alkyl, phenoxy group, benzyloxy, phenyl or contain phenyl, the benzyl of alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, halogen, nitro substituent, and the group represented of following general formula:
Figure C2003101050790003C2
R wherein 10, R 11Be methyl; Work as R 3, R 4, R 5, R 6, R 7, R 8When being hydrogen, B is not NH.
5, according to any described compound among the claim 1-4, it is characterized in that: the compound of general formula (I) is reacted under alkaline condition by the Benzofurantone compound of the hydroxyl shown in benzyl halogen shown in the formula (II) and the formula (III) and makes:
Figure C2003101050790003C3
In showing, Z is a leavings group; Other each groups such as claim 1 definition.
6, described compound of claim 1 and steric isomer thereof are in the application of the various pest on crop of control.
7, the application of described compound of claim 1 and steric isomer thereof germ on the various crops of control.
8, a kind of desinsection, fungicidal composition is characterized in that: contain described compound of claim 1 and steric isomer thereof in the composition, the weight percentage of active ingredient is 0.1-99%.
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JP2007510674A (en) 2007-04-26
EP1683792B1 (en) 2016-07-20
EP1683792B9 (en) 2016-10-05
CN100363356C (en) 2008-01-23
WO2005044813A1 (en) 2005-05-19
US7642364B2 (en) 2010-01-05
EP1683792A1 (en) 2006-07-26
CN1823052A (en) 2006-08-23

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